Discovery and characterization of a novel perylenephotoreductant for the activation of aryl halides

To develop a photocatalyst with catalytical activity for substrates with low reactivities is always highly desired. Herein, based on the principle of structure-property relationships, we rationally designed the natural product cercosporin, the naturally occurring perylenequinonoid pigment, to develop a novel organic perylenephotoreductant, hexacetyl reduced cercosporin (HARCP), through structural manipulation. Compared with cercosporin, HARCP shows prominent electrochemical and photophysical characteristics with greatly improved photoreductive activity, fluorescence lifetime and fluorescence quantum yield. These properties allowed HARCP as a powerful photoreductant to efficiently realize a series of benchmark reactions, including photoreduction, alkoxylation and hydroxylation to construct C-H and C-O bonds using aryl halides as substrates under mild conditions, all of which have never been achieved by the same photocatalyst. Thus, this study well supports the notion that the principle between structural manipulation and photocatalytic activity is of great significance to design customized photocatalysts for photoredox chemistry. (c) 2021 Elsevier Inc. All rights reserved.

Automated summary

By rational design and structural manipulation, a novel organic perylenephotoreductant, hexacetyl reduced cercosporin (HARCP), with greatly improved photoreductive activity, fluorescence lifetime, and fluorescence quantum yield, was developed. HARCP efficiently realized various benchmark reactions under mild conditions, demonstrating the significance of structural manipulation in designing customized photocatalysts for photoredox chemistry.